Process of color photography utilizing immobile 2-substituted-1-naphthylamines



v i invention. i

?atented Nov. 14, 1944 imn'so STATES ATENT PROCESS OF COLOR PHOTOGRAPHY UTI- LIZING IMMOBILE. 2-SUBSTITUTED-1- NAPHTHYLAMINES David W. Woodward, Wilmington, Del, assignor to E. I. du Pont de Nemours '& Company, Wilmington, Del., a corporation of Delaware No Drawing. I Appl cation November 4, 1942, 'Serlal N0. 464,532

- ll claims. .(Cl. 95-6) This invention pertains to photographic elements and compositions containing basic alphanaphthylamines having a blocked 2-position and to processes of producing colored or dye images utilizing the same. More particularly, the invention pertains to photographic elementsbearing a light sensitive stratum and a stratum containing a basic alpha-naphthylamine having in the 2- position an atom or group which by blocking ortho dye coupling directs coupling para to the amino group. The invention also relates to color yielding elements bearing a water Permeable stratum containing such a 2-substituted l-aminonaphthalene dye intermediate which may be intimately associated with a photosensitive layer and to photographic color coupling developer or a reducing solutions containing such dye intermediates and to processes of color photography involving color development and/or azo coupling steps.

'Processes of color photography are known red to blue are obtained. These have the structural formulae:

(A) NRi N=NAr (B) NR:-

N=NAr wherein colored or dye images are formed in photographic elements by treating photographic elements containing reducible images with color coupling developing agents in the presence of dye intermediates. Processes involving the preparation of azo dye images by 'azo coupling procedures combined with development steps are also known. The dye intermediate may be present in water permeable colloid layersor in developer solutions in such processes, When the dye intermediates are used in colloid layers the compounds should be immobile or fast to diil'usion in such layers. v p

'- This invention has for an object the provision of novel dye intermediate in the above described processes of color photography. A further object is to provide color yieldingv elements containing dye intermediates which will yield azo dyes of good spectral color for processes of multicolor photography. Another object is to provide basic alpha-naphthylamines having a coupling blocked Z-positlon, that. is, Z-substitutedbasic alpha-' naphthylamines. for the production of dye image 'in photographic elements by color coupling development and/or azo coupling steps. .A fur- ;ther object is to provide dyes from substituted .alpha-naphthylamines which are of improved color. Anotherobiect isv to immobilize, basic 1- aminonaphthalene dye intermediatescontaining @a blocked 2-.po'sition. Still other objects will be apparent from the following description of the 1 when 'azo, dyes are prepared by coupling dias zotized-wamines; such-as those from p-nitro- .nniline and its substitution-"products with alphanaphthylamines, dyes ranging in shade from Ar is aromatic. R is hydrogen, alkyl or substituted alkyl. Thus coupling occurs either ortho or para to the amino group and the dye obtained is usually a mixture of the two isomeric forms.

The para dye (A) is slightly. more saturated, brighter, and deeper, i. e., shifted to give bluer or greener dyes and hencespectrally more de- 10,. 1942, since there are few dye intermediates.

available which form both quinoneimine dyes on chromogenic development and blue green monoazo dyes on azo coupling as is required in the processes of those applications.

The basic alpha-naphthylamine. dyeintermediates of this invention/contain the following I nucleus:

. Y V wherein R and R. may be'the same or different .and' represent hydrogen, alkyl,. or substituted alkyl and-X, the group which blocks ortho coupling, is a member of the group consisting, of hydrocarbon radicals including alkyl, aryl, or aralkyl. and hydrocarbon radicals connected by or containing an ether linkage. R and R, for example, may be alkyl, e. g., methyl, ethyl,

an amide group which is in turn connected to the amino nitrogen through a methylene (CH2-) group as in Examples I. and IV. In this formula the 4-position is reactive, that is, Y is hydrogen or a reactive or replaceable atom or radical such as a halogen atom or a free sulfonic acid or carboxylic acid group. R. or B may together with X form part of a heterocyclic ring system.

In the above formula the benzene nucleus I may be unsubstituted or may contain various substituents used in dyes and dye intermediates to modify shade and/or solubility which do not promote coupling, such as hydrocarbon radicals, ether groups'and halogen atoms and sulfonic acid or carboxylic acid groups. One or more of such groups may be present in nucleus I in the 5, 6, '7, or iii-positions.

v In a preferred aspect of the invention the dyes contain in ring I at least one solubilizing group such as a sulfonic acid group or acarboxylic acid group and the entire dye intermediate has a molecular weight of at least 300. It has been found that the solubilizing groups (which may be present either in the naphthylamine nucleus or as a substituent on a side chain) render the compounds soluble in aqueous solutions, especially in aqueous alkaline solutions. Thus, the preferred products all give clear colloidal dispersions or solutions to the extent of at least 1 g. in 100 g. of- 2% sodium carbonate solution. These groups also render these compounds compatible with gelatin or similar water permeable colloids but at the same time the high molecular weight of over. 300 makes the compounds fast to diffusion or immobile in such colloid layers during processing.

The alpha-amino group must, of course, be basic if the product is to be a dye intermediate. Thus, when such an amine group is substituted by an acyl radical, for example, alpha-acetamino-Z-methylnaphthaIene, dye coupling does not occur under ordinary conditions as the acetamine group lackssumcient basicity to be a coupling directive group. The alpha-naphthylamine in.

question is sufliciently basic if it will form a salt in IN hydrochloric acid. Thus the alpha-amides and aryl-substituted amines of naphthalene do not form such hydrochloric acid salts and are not considered as dye intermediates or coupling components in this invention. It is also intended that this alpha-amino group be the only coutent of 1 part in 200 parts or developer, are suitable for use with color coupling developing agents, including primary aromatic amino developing agents, hydrazines, etc. In the most useful aspect of this invention, however, higher molecular weight colloidal dye intermediates are referred, as these may be placed in the film element without danger of their migration to other areas.

These radicals may further con-' The lower molecular weight basic alpha-naphthylamines can be convertedinto higher molecular weight compounds in a number of ways. One of the preferred methods is described in the application Serial No. 450,146, filed July 8, 1942, and

application Serial No. 395,496, filed May 27, 1941, by J. E. Kirby and D. W.- Woodward. This method involves introducing an amine-containing substituent onto the aromatic nitrogen atom through a methylene group and subsequently acylating the external amino group with a high molecular weight organic acid, a polymeric acid, or a polyacid or derivative thereof, including the halide or .ester thereof. Thus, derivatives of stearic acid, phthalic acid, octadecylsulfonic acid, polyacrylic acid, or polymerizates of maleic anhydrides with vinyl compounds may be employed.- The above mentioned applications contain a comstituted alkyl chloride or bromide of 8 to 18 car-- bon atoms. Also an aliphatic haloacld, that is, chloroacetic acid maybe condensed in the same way to form the naphthylaminoacid which can in turn be' converted to an amid by reaction with a high molecular weight amine. Likewise an aliphatic haloacetal, e. g., chloropropionaldehyde diethylacetal can be reacted with the naphthylamine to form a compound which may be converted by acetal interchange into a polyvinyl acetal by the method of application Serial No.

233,480,-flled October 5, 1938, by Borough 8; Mo-

. amine.

decylamine, cyclohexylamine, or amino-cellulose. Following such amide formation, the 1-nitro Queen, now U. S. P. 2,310,943.

A further alternative is to convert a l-acetamino-2-substituted naphthylamine-5,6, or -7- sulfonic acid with chlorosulfonic acid or phos-,-

5 weight of polymeric amine to form the sulfur:-

amide following whichthe acetamino group is hydrolyzed. Alternatively, a 1-nitro-2-substituted naphthalene-5, 6, or 'I-carboirylic acid or 1-nitro-2-naphthoic acid may be treated with phosphorus pentachloride to form the acid chloride which is then converted to an amide by reaction with a high molecular weight'or poly- Such amines include octylamine, octagroup is reduced to form the alpha-naphthylamine containing a carbonamide group. The alpha-amino group may be alkylated if desired. Other known methods of immobilization may be employed.

, While X in the representative formula is preferably hydrocarbon or hydrocarbon containing an ether linkage, for example, alkoxyl, other organic radicals which cause only minor changes in the physical and chemical properties of thecan be used as dye intermediates orin the prep aration of immobile dye intermediates in the photographic compositions, articles, and processes aseae e of this invention include the following alphanaphthylamines:

2-methyl 4-chloro-2-methyl 2-carboxy1ic acid and esters and amides 2-nitro 2-chloro 2nitro-4-bromo 2,2f-dinaphthyl derivathereof tive 2-methoxy N-methyl-z-nitro 2-ethoxy N-ethyl-2-nitro 2-methoxy 6 sulfonic 2-methyl-4-bromo acid 2-methyl-8-chloro 2-ethoxy-6-sulfonic acid 2-nitro-3-chloro In addition, many heterocyclic compounds, some. of which also possess sufiicient molecular size to render them immobile in film elements also may be used in this invention; Some of these are included in the following list:

' hydride (70, i, 8, 9,

10, 100) (see Chemical Abstracts, Decennial Index 1027-1936, page 3644, column 3). C3 H,

Gamnia-benzophenoxazine hexa- CH; hydride (8a, 8, 9, 10, ll, llu) (seeChemicai Abstracts, De- 1' CH; cennial Index 19274938, page 3675, column 1). Hz

l,2,3,4-tetrahydro-7,8 benzoquin- Ell I oline. I N Cg i OH: I C

Lil-din dro-4-naphth(l,2-.d)-m H oxszi e (see Chemical Ah: I stracts, Decennial Index 1027-- N--CH, 1936, page 6125, oolnmn 1). \0

-Cfi2 Preferably the alpha-naphthylamines have a lower- (1 to 4 carbomalkyl or alkoxy group in the 2-position.

The invention will be further illustrated but is not intended to be limited by the followin examples:

Example I.-Reaction of 1-amino-2-methoxynaphthalene-fi-sulfonic acid (amino-Schaefiers acid methyl ether) with p-acetaminophenoxyethyl bromide followed by hydrolysis and condensation with a styrene maleic anhydride polymer (these reactions are all described in the application of J. E. Kirby and D. W. Woodward, Serial No. 450,146, filed July 8, 1942) yields an immobile dye intermediate having the following probable unitstructure:

0H5 OOH O I IHO -OmOHi-NH A 1.7 gram sample of this material is dissolved in '11 g: of 5% sodium carbonate and mixed with 100 parts of a red-sensitive silver iodobromide emulsion sensitized with 2-ethyl-alphanaphthselenocarbocyanine 3 ethiodide. This emulsion may be then us d n place of emulsion (1) of Example I of Woodward application Serial No. 450,403, filed July 10, 1942. 'This application deals with the production of natural color pictures by the 820 reversal method. When the resulting film is processed according to that invention, that is, exposed to controlled light, developed with an aromatic primary amino developing agent, coupled in the unexposed areas with v diazotized 2,4-dinitro-aniline, the primary color 40 developed areas bleached, and the silver and silver halide removed, a full color reproduction is obtained: The above dye intermediate contributes the blue-green part image and replaces the 'l-amino-5-naphthol-derivative of that example. This provides an excellent example of p the effect of the Z-substituent on dyes produced from a alpha-naphthylamines. If the corresponding dye intermediate containing hydrogen in the 2-posltion in place of methoxy group is bluegreen.

Example H.-Ten parts of alpha benzocarba'zol hexahydride (7a, 7, 8, 9, 10, 10a) is dissolved in 100 parts of ethyl alcohol and mixed with 900. parts of a gelatino silverbromide-iodide photographic emulsion containing 10 to 12% solids and are coated on a suitably subbed cellulose acetate film base. A sample of the film can be exposed by controlled light, developed in a 4 aminodiethylaniline developer and bleached and fixed -.by the customary procedure whereby a magenta dye image is formed.

Films prepared in this way can be treated with aqueous. diazonium solutions of pH 1-7, with fixing prior or subsequent to such treatment, to

yield clear, brilliant azo dyes. -When this film is treated with a. solution of diazotized 4-nitro- 2-chloro-aniline a blue dye is formed.

Example IIIQ-To 100. cos. of a developer so1u-,

tion of the following composition:

7 Water cubic centimetersused, a red-blue" dye is obtained instead of a are added from to 100 mg. of sodium 1-amino-= 2-methoxy-naphthalene-6-sulfonate dissolved in a few cos. of water.

was then developed in such a solution washed, bleached, fixed and washed, whereby a magenta dye image remained.

Example IV.One molar equivalent of l-hydroxy-Z-methylnaphthalene, 1 equivalent of water, 0.1 molar equivalent of sulfur dioxide, and 3 molar equivalents of ethylenediamine are heated and agitated in a closed container under pressure at 160 C. for 6 hours, the excess of diamine removed under reduced pressure, the residue washed with water and distilled under reduced pressure to yield 1-(beta-aminoethyD-amino-2- methylnaphthalene which is then condensed in acetone solution with an ethylene-maleic anhydride polymer (see reference cited in Example I for complete directions) to yield a product having the following probable structure:

where X is the number of units in the chain.

This material may be added to a photographic emulsion after the method of incorporation given in Example 1. Such films, when color devel- A photographic element: containing exposed silver bromide iodide salts utilized. I

A large number of color developing agents con- I taining an unsubstituted amino group may be used to form indamine dyes with the compounds of this invention. Suitable agents are described in U. S. Patents 2,182,815, 2,189,817, 2,191,037,

oped with a solution of p-aminodiethylaniline,

.yield images of a bright magenta color. When the films are treated with diazotized 2-4-dinitroaniline a blue-green dye is formed. This material has uses similar to' the product of Example I.

In place of the 2-substituted-alpha-naphthylamine of the above examples other basic 2-substituted-alpha-naphthylamines canbe substituted having the structure set forth in formula (1) above. When the intermediate is to be used for chromogenic development as with an aromatic primary amino developing agent such as paminodiethylaniline, it is necessary to have one of the R's of the formula (1) a hydrogen atom, since the dyes formed have the quinoneimine structure. The preferred intermediates which are to be' used in colloidal .layers should be of suflicient molecular weight (at least 300) to make them immobile therein. The groups which increase the size or molecular weight suflicient to cause immobility may be attached through the nitrogen atom (providing its basicity is maintained) or through any ring position excepting the 4-position which must remain available for coupling.

Other useful methods of immobilization include introducing reactive groups includin hyand 2,200,924. Still other suitable color coupling developing agents are described in U. S. P. 2,163,820 and British Patent 541,649. The silver salt image can also be developed with hydrazine developers in like manner to produce azo dye images. Suitable developers are described in U. S. Patent 2,220,924 and British Patent 545,443. In addition, a silver halide emul-' sion containing one of the herein described intermediates which has been exposed and treated to develop the silver ,image and fixed can be bleached and treated with a diazo or tetrazo salt and converted into a color image by the process of U. S. P. 1,517,049.

Other types of organic colloi'ds can be used as binding agents for these photographic elements containing the herein' described products. Suitable colloids exhibiting high viscosity characteristics and appreciable gel strength which are compatible with these novel dye intermediatesinclude albumin, agar-agar, Irish moss, cellulosic derivatives, synthetic resins such as polyvinyl acetals, etc.

The dye intermediates used not be placed directly'in the light-sensitive layers but may be used in separate layers which are in operative association therewith. Thus, they can be in corporated in a separate gelatin or other waterpermeable colloid layer which is superposed on the light-sensitive layer or spaced therefrom by droxyl, amine, aldehyde, thiol, sulfonyl chloride and carboxyl groups into the molecule, preferably on a side chain, such as on one of the basic nitrogen substituents, these then are caused to react with appropriate compounds to form higher molecular weight' ethers, esters, amides, substituted amines, vinyl compounds, sulfides, sulfones,

- etc.

. Compounds suitable for use in preparing the immobile types are quite numerous and representative ones are listed above. The methods used for immobilizing dye intermediates havingsimilar groups which have been described in the literature are applicable to the compounds of this In addition, they maybe incorporated in color yielding elements of the type set forth in Murray application Ser. No. 370,195, filed Dec. 14, 1940,

and Sease 8: Murray application Ser. No.'370,194, filed Dec. 14, 1940 now U. S. P. 2,328,034. To be more specific, the dye intermediates can be used in colloid layers of elements free from a photo sensitive stratum or containing such strata in a position so that it does not coact with the colloid layer. v

The compoundsof this invention which contain suificiently large groups on the side chain to increase the molecular weight to 300 or greater and thus render the product immobile in a photographic film are of use in producing colored pictures by the method described in U. S. Patents 1,055,155, 2,178,882, 2,179,228, 2,179,238, 2,179,239

and in the process of Woodward U. S. application Ser. No. 335,416, filed May 15,1940, now

These compounds may be used in comunction with various types of reducible silver halides such as silver chloride, silver bromide, silver chlorobromide, etc., images, latent images, bleached silver images such as silver ferrooyanide, silver copper chloride} silver chromium chloride, as well as silver chromate and other water insoluble silver salts. Images produced by the exposure of bichromated gelatin are also reduced by the color forming development procedure described above.

Other uses for these products include the preparation of filter dyes andnon-halation dyes to be used with photographic films. These intermediates and the dyes produced from them can also be used in the catalytic silver bleach process as described in U. S. P. 2,020,775 and can be used sisting of hydrocarbon radicals and ether interto produce dyes, pigments, and colored textiles,

especially by the process of Kirby application Ser. No. 411,261 and Woodward application Seg'. No. 411,262, filed September 1'7, 1941.

As many widely different embodiments of this invention may be made without departing from the spirit and scope thereof,'it is to be understood .that the invention is not limited to the specific embodiments thereof except as defined in the appended claims. t

I claim: a 1. The process which comprises developing'a silver salt image in the presence of a basic alphanaphthylamine having in the 2-position a radical taken from the group consisting of hydrocarbonradicals and ether interrupted hydrocarbon radicals, with a color couplingdeveloping agent.

2. The process which comprises developing a 1 permeable colloid layer containing a dye inter.- mediate of the generalformula:

- Hit chi-R wherein R is a radical taken from the group conrupted hydrocarbon radicals containing at least five carbon atoms and X is a member of the group consisting of hydrocarbon radicals and.

ether interrupted hydrocarbon radicals.

8. A color-yielding element comprising-a base having superposed thereon at least one waterpermeable colloid layer containing a dyeintermediate of the general formula:

- HN-CHz-R wherein R is a radical taken from the group conphotographic element containing at least one layer containing a reducible silver saltimage in the presence of a basic alpha-naphthylamine having in the 2-position a radical takenfrom the group consisting of hydrocarbon radicals and ether interrupted hydrocarbon radicals, with a sisting of hydrocarbon radicals and ether interrupted hydrocarbon radicals containing at least one carbon atom and X is a member of the group consisting of hydrocarbon radicals and ether interruptedhydrocarbon radicals, said radical R being further characterized in that it contains color coupling aromatic primary amine developsensitive silver salt layer and at least one waterpermeable colloid layer containing an immobile basic alpha-naphthylamine having in the 2-position a radical taken from the group consisting of hydrocarbon radicals and ether interrupted hydrocarbon radicals.

5. A color-yielding element as set forth inclaim 4 wherein the naphthylene nucleus contains a solubilizing group taken from the class consisting of carboxylic and sulfonic acid groups.

6. The process which comprises developing a silver salt image in the presence of a basic alphanaphthylamine having in the 2-position a radian immobilizing group consisting of a monoamide of a polymeric acid.

9. A color-yielding element comprisinga base having superposed thereon at least one water-- permeable colloid layer containing a dye intermediate of the formula:

10. A color-yielding element comprising a base I. having superposed thereon at least one watercal taken from the group consisting of hydrocarbon radicals and ether interrupted hydrocarhon radicals, with a color coupling agent, reacting the resulting element with a diazotized amine, decolorizing the dyes formed during the color coupling development and removing the silver and silver salts.

J '7. A color-yielding element comprising a base having superposed thereon at least one waterpermeable colloid layer containing'a dye intermediate of the formula:

where X is the number of units in the chain.

11. A color-yielding element comprising a base having superposed thereon at least one waterpermeable colloid layer containing a dye intermediate of the formula:

I l-C H:

I CH:

DAVID W. WOODWARD.

page 2, second column, -11nel .5,.for "weight of" read.--we1ght or-' CERTIFICATE OF coRREcTIon.

Patent fi 2,362,519. November 12;, 19%.

DAVID w. WOODWARD.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows Page 1, first column, I lines 29 and 36, for, the word intemediateread --1ntermed1ates second column, line 147, before "alpha" strike out ".a ;,line 14.9, for "methoxy" read ---methoxyl--; pege 14., second column, line 14.1, for "used" read --need--;

and that the said Letters Patent should be read with this correction therein that the same may confom to the record of the case in the Patent Office.

Signed and' sealed this 27th day of Febmery, A. n. 1915 Leslie Frazer (Seal) Acting Commissioner of Patents. 

